Application of Carbon Nanomaterials in Lithium-Ion Battery Electrodes

Carbon nanomaterials such as single-walled carbon nanotubes (SWCNTs) and graphene have emerged as leading additives for high capacity nanocomposite lithium ion battery electrodes due to their ability to improve electrode conductivity, current collection efficiency, and charge/discharge rate for high power applications. In this work, the these nanomaterials have been developed and their properties have been fine-tuned to help solve fundamental issues in conventional lithium ion battery electrodes.;Towards this end, the application of SWCNTs in lithium-ion anodes has been studied. As-grown SWCNTs possess a distribution of physical and electronic structures, and it is of high interest to determine which subpopulations of SWCNTs possess the highest lithiation capacity and to develop processing methods that can enhance the lithiation capacity of underperforming SWCNT species. Towards this end, SWCNT electronic type purity is controlled via density gradient ultracentrifugation, enabling a systematic study of the lithiation of SWCNTs as a function of metal versus semiconducting content. Experimentally, vacuum filtered freestanding films of metallic SWCNTs are found to accommodate lithium with an order of magnitude higher capacity than their semiconducting counterparts. In contrast, SWCNT film densification leads to the enhancement of the lithiation capacity of semiconducting SWCNTs to levels comparable to metallic SWCNTs, which is corroborated by theoretical calculations.;To understand the interaction of the graphene with lithium ions and electrolyte species during electrochemical we use Raman spectroscopy in a model system of monolayer graphene transferred on a Si(111) substrate and density functional theory (DFT) to investigate defect formation as a function of lithiation. This model system enables the early stages of defect formation to be probed in a manner previously not possible with commonly-used reduced graphene oxide or multilayer graphene substrates. Using ex situ and Ar-atmosphere Raman spectroscopy, a rapid increase in graphene defect level is detected for small increments in the number of lithiation/delithiation cycles until the I(D)/I(G) ratio reaches ∼1.5-2.0 and the 2D peak intensity drops by ∼50%, after which the Raman spectra show minimal changes upon further cycling. Using DFT, the interplay between graphene topological defects and chemical functionalization is explored, thus providing insight into the experimental results. In particular, the DFT results show that defects can act as active sites for species that are present in the electrochemical environment such as Li, O, and F. Furthermore, chemical functionalization with these species lowers subsequent defect formation energies, thus accelerating graphene degradation upon cycling. This positive feedback loop continues until the defect concentration reaches a level where lithium diffusion through the graphene can occur in a relatively unimpeded manner, with minimal further degradation upon extended cycling. Overall, this study provides mechanistic insight into graphene defect formation during lithiation, thus informing ongoing efforts to employ graphene in lithium ion battery technology.;Having understood the electrochemical properties of graphene, we have used this to improve the performance of Li-ion cathodes. In particular, Spinel-structured LiMn2O4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, thermal stability (safety) and high power capability. However, LMO suffers from a limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, we show that a single sheet of graphene can act effectively as a diffusion barrier for Mn2+ ions, thereby protecting the cathode surface and significantly reducing the dissolution process. Relative to lithium cells containing a sputtered and uncoated thin film LMO 'control' cathode, cells with a graphene-coated LMO cathode provide approximately three times the capacity with significantly superior cycling stability and power. X-ray photoelectron spectroscopy (XPS) depth profiling provides evidence that the graphene coating inhibits manganese depletion from the LMO surface. Furthermore, cross-section transmission electron microscopy (TEM) demonstrates that a stable solid electrolyte interphase (SEI) layer is formed on graphene, which screens the LMO from direct contact with the electrolyte, thereby prolonging the electrode life. Density functional theory (DFT) calculations support the hypothesis of graphene as a diffusion barrier: Defected graphene acts as a barrier for manganese diffusion while allowing the transport of lithium. However, DFT calculations also suggest that the role of graphene goes beyond a physical barrier. The reactive edge of graphene can chemically interact with Mn3+ at the electrode surface, promotes an oxidation state change (Mn3+→Mn4+) and suppresses dissolution and the Jahn-Teller distortion associated with Mn 3.